|Publication number||US5705554 A|
|Application number||US 08/499,834|
|Publication date||6 Jan 1998|
|Filing date||10 Jul 1995|
|Priority date||25 Mar 1994|
|Also published as||EP0675177A2, EP0675177A3|
|Publication number||08499834, 499834, US 5705554 A, US 5705554A, US-A-5705554, US5705554 A, US5705554A|
|Inventors||Ti Chou, James Stanley Dodge, George Kletecka|
|Original Assignee||The B.F. Goodrich Company|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (8), Referenced by (8), Classifications (17), Legal Events (5)|
|External Links: USPTO, USPTO Assignment, Espacenet|
This is a continuation of application Ser. No. 08/217,995 filed Mar. 25, 1994, now abandoned.
This invention relates to a heat resistant coating composition comprising a water soluble or water-dispersible resin which contains a sufficient number of either carboxyl groups or carboxyl and amide groups which will form anhydride rings or imides, in the presence of heat and a latex polymer emulsion, where the polymer has a particle size of less than 1600 Angstroms, and where the overall aqueous system contains an effective mount of nitrogen-containing volatile base, to achieve a pH of greater than about 7.5 and to keep the resin solubilized or dispersed. The coating can be used, for example, as an overcoat or overprint varnish for inks on packaging materials or other coating cases where heat resistance is desirable.
Heat resistant coatings have particular applicability to the field of graphic arts and packaging. Heat resistant polymer coatings are used as overcoats or overprint varnishes for inks on packaging materials. Paper goods such as paper plates and cups employed for hot foods also require heat resistant coatings.
In the manufacture of graphic arts products and paper goods, one process involves the printing of the graphic materials on a substrate and combining the printed material with structural materials, such as corrugated backing to form a package or other useful structure. The laminating process which is used to attach the structural layers usually involves high temperatures for the bonding process. It is in applications such as these where the coating polymer should have good heat resistance properties to avoid damaging the printed materials. In addition, other characteristics of the polymer, which would be important if it is used as an overcoat, include the water-resistance of the polymer, the skid angle of the coating and the gloss of the coating since these are important to the appearance of the printed matter.
Materials are known for use as heat resistant coating compositions, but frequently they suffer from disadvantages in the balance of their properties. Conversely the materials may provide good coating properties, but suffer from poor heat resistance. For example, in U.S. Pat. No. 4,358,573, there is disclosed a method for solubilizing a terpolymer of maleic anhydride and mixtures of lower and higher alkenes employing an aqueous solution of ammonium hydroxide to form a coating polymer. However, the films formed from such polymers lack enhanced heat resistance and become tacky during storage and use. U.S. Pat. Nos. 4,623,692 and 4,730,019 disclose a coating composition having improved heat resistance which employs a combination ligand-free monomer and maleic anhydride polymer with an effective mount of a metal ion-containing fugitive ligand complex solubilized in an aqueous medium. In the presence of heat, the metal ion will effectively crosslink the polymer and provide the heat resistance desirable in the polymer. But, the preferred metal ion is zinc and there has been some resistance to having the zinc ion present in the packaging coatings.
A commercially available material which is suggested for use as a clear over-varnish and as a general purpose ink resin is sold by Rohm and Haas Company under the tradename Emulsion E-2183. It is described as an acrylic aqueous polymer useful where the underlying inks must be protected from heat during subsequent converting steps. It is believed to be a blended polymer of an acrylate latex and a maleic anhydride copolymer in a ratio of 40:60 parts of latex to parts of maleic anhydride copolymer, having an acid value of about 150 and a particle size of between about 180 to 230 nanometers (nm) or 1800 to 2300 angstroms (A°).
The present invention has resulted from the discovery that a heat-resistant coating composition having a good balance of other properties, including water resistance, skid angle, and gloss, can be achieved by employing a composition which is a combination of a water soluble or dispersible resin containing a sufficient number of either (a) carboxyl groups or (b) carboxyl and amide groups and an aqueous latex polymer emulsion, where the particle size of the latex polymer is less than 1600 Angstroms and the emulsion contains an effective amount of nitrogen-containing volatile base to achieve a pH of greater than 7.5 and to keep the resin solubilized or dispersed. The preferred resin is a maleic anhydride copolymer and the preferred latex polymer is a (meth)acrylate polymer or copolymer. The weight ratio of resin to latex polymer emulsion is between 50-95:50-5, with the range 60-80:40-20 being preferred, and the ratio 65:35 being further preferred.
In the present invention the coating composition is produced preferably by polymerizing the latex polymer in the presence of the water-soluble or water-dispersible resin. This results in a composition which contains a carboxyl-containing (optionally also amide-containing) resin and a latex polymer emulsion having a particle size of less than about 1600 Angstroms or A° (or 160 nanometers or nm), preferable less than 150 nm, with less than 100 nm being further preferred.
There is nothing critical in the latex polymerization process and so it can be done in a typical process such as for example that disclosed in U.S. Pat. No 4,956,434, the teachings of which are incorporated herein by reference. Although, other latex processes could be employed. By polymerizing the latex in the presence of the carboxyl containing resin, the use of surfactants can be minimized or eliminated, a latex product is produced having an average particle size of less than about 160 nm and the result is a coating having a good balance of properties.
It is important that the overall aqueous system contains an effective amount of a nitrogen containing volatile base, such as ammonia, an amine, or other volatile base to achieve a pH of greater than 7.5 and to keep the resin solubilized or dispersed. Ammonia is the preferred volatile base, but the following amines could be employed:
The carboxyl containing resin is a water soluble or water dispersible resin which contains a sufficient number of either carboxyl groups or carboxyl groups and amide groups so that in the presence of heat, anhydride rings or imides will form and water will be given off to provide the coating with improved heat resistance. The preferred carboxyl-containing resin is a maleic anhydride (MA) copolymer, preferable with styrene. Other maleic anhydride copolymers can be employed, such as MA with diisobutylene or with methyl vinyl ether. Examples of other carboxyl containing polymers include (meth)acrylic acid, itaconic acid, or fumaric acid or combinations of these carboxylic acids polymerized with styrene and/or alpha methyl styrene and polymers and copolymers of (meth)acrylic acid and amides, such as acrylamide, t-octyl acrylamide, t-butyl acrylamide, and/or acrylates, such as isobutyl, n-butyl-, or stearyl-(meth)acrylate. Alternatively, blends of carboxyl-containing resins could be employed.
The latex polymer emulsion can be prepared from a variety of monomers, including (meth)acrylate monomers. The proportions of the various monomers are adjusted to yield polymers with glass transition temperatures (Tg) of less than or equal to 50° C.
(Meth)acrylate monomers include methyl acrylate, ethyl acrylate, propyl acrylate(s), butyl acrylate(s), 2-ethylhexyl acrylate, n-octyl acrylate, methyl (meth)acrylate, butyl (meth)acrylate, octyl (meth)acrylate, and the like. The (meth)acrylate monomers can be polymerized together, or with other monomers including the conjugated dienes such as butadiene and isoprene; α-olefins such as ethylene, propylene and isobutylene; vinyl halides such as vinyl fluoride, vinyl chloride and vinylidene chloride; vinyl esters such as vinyl acetate; vinyl aromatics such as styrene, α-methyl styrene; vinyl toluene and vinyl naphthalene; alkyl vinyl ethers such as methyl vinyl ether, propyl vinyl ether, and the like.
In addition to polymers which include (meth)acrylate monomers and the above monomers, a large variety of other copolymers of the above monomers are possible, including styrene with one or more of the dienes, e.g. butadiene, vinyl acetate or other vinyl esters with vinyl chloride, and the like.
All the various possible latexes listed above may also contain minor amounts (less than about 25%) of functional monomers such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, acrylonitrile, N-methylol acrylamide and the like.
In addition, combinations or blends of latex polymers or copolymers can be used with (meth)acrylate latexes being preferred. A further preferred latex is butyl methacrylate copolymerized with 2-ethylhexyl acrylate and styrene, although the styrene is optional. Other (meth)acrylate latexes to be used include lauryl(meth)acrylate. Other combinations of latex polymers can be employed, so long as the latex has a Tg of 50° C. or less.
The ratio of carboxyl containing resin to latex polymer emulsion will be in the range of 50 to 95 parts per hundred resin (phr) of carboxyl-containing resins to 50 to 5 phr of latex polymer emulsion with a 60-80 to 40-20 range being further preferred, and a 65:35 ratio being preferred.
Thus, preferred composition comprises 65% by weight (solids content) or parts per hundred resin (phr) of the water-soluble or water-dispersible resin and 35% by weight (solids content), or phr, of the latex polymer, with the preferred latex polymer being a (meth)acrylate polymer containing butyl methylacrylate, 2-ethyl hexyl acrylate, and styrene.
Into a 4-neck, three liter glass resin kettle equipped with a stirrer, condenser, thermocouple and gas inlet tube was added 65 parts by weight of a styrene maleic anhydride resin, such as SMA 1000 resin which is commercially available from ELF Atochem North America, Inc., along with the water in which it is dissolved. Another 27 parts of demineralized water is added. Good stirring is maintained throughout the procedure. The pH is adjusted to 9.0 with ammonia. The reactor is closed and a water-cooled condenser is attached. The reactor contents are then heated to the initiation temperature of 85° C. Next, an initiator solution of 1.0 parts by weight of ammonium persulfate and 2.06 parts of demineralized water is prepared. Once the temperature of the reactor contents reaches the initiation temperature, the initiator solution is added to the reactor contents. Approximately 5 minutes after the initiator solution is added, a premix solution of 24.5 parts of butylmethacrylate, 0.35 parts of styrene and 10.15 parts of 2-ethylhexyl acrylate, is metered into the reactor contents over approximately a 3 hour period. The exact time is not critical. The key factor is to meter at a rate so that the heat evolved can be controlled and prevent the reactor contents from overheating. Next, a "booster" initiator solution is prepared from 0.1 part of ammonium persulfate and 1.18 parts of demineralized water and pumped into the reactor. The mixing is continued for an additional period of time, approximately 1 hour or more. After the booster initiator step has been completed, a typical redox procedure is followed or alternatively, the mixing and heating can be continued for approximately an additional hour, and the latex is ready for packaging and application.
In testing the overprint varnish, the polymer emulsion is compounded with polyethylene wax emulsion, commercially available as Michem Emulsion 39235, and water. The compound viscosity is measured using a #2 Zahn cup. For most practical purposes, the viscosity should be adjusted by water addition to 25-35 seconds as measured using a #2 Zahn cup. The addition of wax emulsion and the adjustment of compound viscosity are general procedures used by the industry.
A No. 4 wire-wound rod, or a Pamarco Flexo Hand Proofer was used to apply the overprint varnish onto solid bleached sulfate (SBS) paperboard which comes pre-coated with a general pigmented paper coating. After coating, the overprint varnish is dried at 350° F. for 1 minute and then tested for gloss, skid angle, and water resistance. For the heat resistance test, the coating is dried at 220° F. for 15 seconds.
In order to evaluate the heat resistance of the varnish, a 400° F. hot iron was applied to the coating surface. This is done, for example, by placing the iron in contact with the surface of the coated paperboard and moving it across the coating surface. To provide good heat resistance, the coating surface should not be damaged and gloss should not be affected. The heat resistance is a visual observation rated from 1 to 8, with 1 being the highest.
The gloss is measured in accordance with ASTM D-523, which is incorporated herein by reference, by placing the coated material under a gloss meter, such as a Byk Chemie Gloss Unit Type 4031/4343, and measuring the gloss at a 60° angle and an 85° angle. Gloss readings will be a number which will range from 0 to more than 100, with the higher number being higher gloss. For the applications discussed herein, a higher gloss is preferred.
In this procedure, two coated paperboards are placed in face-to-face relationship, with the coated surfaces in contact. To one of the paperboards is attached a standard weight by wrapping the paperboard around the weight. The skid angle is measured using a TMI (Testing Machines Inc.) coefficient of friction tester, Model No. 32-25. The machine consists of an inclined plane, whose angle can be varied by a motor and gear assembly, and a sliding weight. One piece of the test specimen is clamped onto the inclined plane. Another piece is clamped around the sliding weight. The incline of the plane is then increased until the weight just starts to slide, at which point the plane is locked and the angle is noted. A high skid angle is desirable. A skid angle of greater than 25° is preferred.
The coated surfaces were tested for wet blocking resistance to determine the water resistance. In the wet blocking test, two pieces of 5×5 inches of coated SBS paperboard were placed together, with coated sides facing each other. Ten drops of water were placed between them. A 70 pound load was applied for one hour. The coated surfaces should not stick together and should not be damaged.
In addition, particle sizes were run using the standard operating procedure for a Brookhaven Instruments Corp. Particle Sizer, Model BI-90. The acid value, which is the milligrams of potassium hydroxide needed to neutralize one gram of resin and latex solids also were obtained for the polymers.
Following the typical example, a series of coatings were made and tested. The process of the typical example was followed except where noted such as Example 1D, which is a commercially available product and Example 2 which is a blended product which is similar to Example 1D. The results are set forth in Table I. The compositions are noted in the Table and the following terms are used to describe the resins and/or latex polymers:
SMA-1000 is the tradename of ELF Atochem North America, Inc. for a copolymer of styrene and maleic anhydride having a ratio of styrene to maleic anhydride of 1:1.
SMA-2000 is the tradename of ELF Atochem North America, Inc. for a
__________________________________________________________________________PolymerExampleCarboxyl Polymer Latex Polymer Ratio Particle Acid Heat Skid Water GlossNo. (Phr) (Phr) CP:LP Size Value Resistance Angle° Resistance 60° 85°__________________________________________________________________________ 1A SMA 1000 (65) 24.5 BMA 65:35 66 312 1 27.5 P 69.0 75.7 10.2 EHA 0.4 STY B Tamol 165 (65) 24.5 BMA 65:35 149 169 1 28.0 P 58.4 82.3 10.2 EHA 0.4 STY C Gantrez AN 119 (65) 24.5 BMA 65:35 874 -- 1 23.0 F 51.8 74.7 10.2 EHA 0.4 STY D E-2183 -- -- 180 170 1 32.3 P 56.2 76.8 2* SMA 1000 (65) 24.5 BMA 65:35 280 312 1 28.8 P 40.1 52.3 10.2 EHA 0.4 STY 3A 32.5 SMA 1000 24.7 EHA 57.5:42.5 78 244 5 30.5 P 61.2 84.825.0 SMA 2000 17.8 STY B 32.5 SMA 1000 18.7 EHA 57.5:42.5 67 244 6 29.5 P 59.8 85.025.0 SMA 2000 28.8 STY 4A 19.5 SMA 1000 32.7 BMA 54.5:44.9 69 216 6 26.0 P 54.2 81.835 SMA 2000 12.2 EHA B 45 SMA 1000 32.7 BMA 60:40 75 271 1 24.5 P 62.7 87.015 SMA 200 12.2 EHA C 32.5 SMA 1000 30.5 BMA 57.5:42.5 72 244 3 25.0 P 57.4 84.125 SMA 2000 12 EHA 5A 37.5 SMA 2000 27 BMA 62.5:37.5 64 198 1 27.0 P 50.9 77.025 Tamol 165 10.5 EHA B 37.5 SMA 2000 27 BMA 62.5:37.5 64 251 1 26.5 P 49.6 73.225 SMA 1000 10.5 EHA C 62.5 SMA 2000 27 BMA 62.5:37.5 64 219 1 31.3 P 50.2 74.0 10.5 EHA D 25 SMA 2000 30.5 BMA 57.5:42.5 80 244 3 29.5 P 58.4 83.532.5 SMA 1000 12 EHA 6A 30 SMA 1000 28.8 BMA 60:40 87 249 3 27.8 P 60.0 84.530 SMA 2000 11.2 EHA B 60 SMA 1000 28.8 BMA 60:40 70 288 5 29.5 P 62.6 86.1 11.2 EHA C 60 SMA 2000 28.8 BMA 60:40 58 210 3 31.3 P 46.6 71.4 11.2 EHA 7A 32.5 SMA 1000 30.6 BMA 57.5:42.5 76 244 6 30.0 P 56.0 78.825.0 SMA 2000 11.9 EHA B 32.5 SMA 1000 42.5 LMA 57.5:42.5 166 244 1 23.0 P 50.9 79.925.0 SMA 2000 8A 65.0 SMA 1000 30.5 BMA 65.35 71 312 1 28.8 P 68.2 89.0 4.5 EHA B 65.0 SMA 1000 20.0 BMA 65:35 68 312 1 24.0 P 65.5 86.1 15.0 EHA 9A 65.0 SMA 1000 25.2 BMA 65:35 69 312 2 25.5 P 66.5 88.0 9.8 EHA B 65.0 SMA 1000 14.0 BMA 65:35 71 312 1 20.5 P 65.2 85.8 21.0 EHA C 45 MAA 16.7 BMA 60:40 55 161 3 24.8 P 48.8 75.430 STY 23.3 EHA25 AMS10 65.0 SMA 1000 35 BMA 65:35 71 312 2 26.7 P 61.2 87.011 45 MAA 23.3 EHA 60:40 87 191 2 29.0 P 53.5 81.115 STY 16.7 STY40 AMS12A 45 MAA 28.8 BMA 60:40 74 153 5 26.0 P 50.1 80.230 STY 11.2 EHA25 MMA B 55 MAA 28.8 BMA 60:40 82 191 3 27.5 P 55.6 83.025 STY 11.2 EHA20 AMS__________________________________________________________________________ * = BLENDED POLYMER
copolymer of styrene and maleic anhydride having a ratio of styrene to maleic anhydride of 2:1.
Tamol-165 is the tradename of Rohm & Haas Company for a copolymer of maleic anhydride and diisobutylene.
Gantrez AN-119 is the tradename for a copolymer of maleic anhydride and methyl vinyl either available from ISP, Inc.
E-2183 is the tradename of Rohm & Haas for an acrylic aqueous polymer used as a clear over-varnish.
BMA means butyl (meth)acrylate
EHA means 2-ethyl hexyl acrylate
STY means styrene
LMA means lauryl methacrylate
MAA means methacrylic acid
AMS means alpha methyl styrene
MMA means methyl methacrylate
Further, in the examples a sample of E-2183 was run as a control to aid evaluation of the results. But, each control result is not reported as it is in Example ID. Instead, it is noted that for all the tests, the E-2183 coating resulted in a heat resistance value which ranged from 1 to 3 and averaged 1.3; a skid angle which ranged from 25.5° to 33.3°, or an average of 28.4°; a 60° gloss varying from 49.9 to 56.2, with an average of 52.2; an 85° gloss which ranged from 76.8 to 83.5 or an average of 81.2; and a water resistance which was acceptable (or passed) in all cases.
As can be seen from the examples, a variety of carboxyl containing resins can be employed, a variety of latex polymers can be employed, and a favorable balance of properties, for example, skid angle, water resistance, and gloss can be obtained in a coating having a good heat resistance when the coating has a latex polymer having an particle size of less than 160 nm.
For example, as seen in Examples 1A versus 1D, a commercially available product, the coating of the present invention had comparable heat resistance, but higher gloss readings since the 60° gloss reading was significantly higher and the 85° gloss readings were about the same. Examples 8,9, and 10 further show that coatings of the present invention achieve high gloss values in addition to heat resistance. Examples 10, 8A, 9A, 8B and 9B show that with the same carboxyl polymer, in the same amount, varying the ratio of BMA to EHA will produce a progressively lower skid angle until a less than desirable, less than 25° angle is achieved. Examples 3-12 demonstrate that various carboxyl-containing polymers or resins can be employed, but that it is desirable to use more than 58% by weight carboxyl polymer, preferably more than 60% by weight. Further, examples 3-8 support the belief that, although the performance of the resin is probably attributable to a combination of sufficient carboxyl groups and their placement, a sufficiently high acid value, e.g. greater than 250, can be a factor in the performance of the carboxyl-containing polymer. Thus carboxyl polymer content or acid value or combinations of these factors influence the performance of the coating. Various latex polymers can be employed and still achieve a good balance of properties.
The foregoing embodiments of the present invention have been presented for purposes of illustration and description. This description and these embodiments are not intended to be exhaustive or to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above disclosure. The embodiments were chosen and described in order to best explain the principle of the invention and its practical applications to thereby enable others skilled in the art to best utilize this invention in its various embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the invention be defined by the following claims:
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|U.S. Classification||524/460, 524/521, 524/517, 524/523, 524/527, 524/522, 524/458, 524/515, 524/525, 524/524|
|International Classification||C09D5/18, C09D201/08, C08F2/16|
|Cooperative Classification||C09D5/18, C09D201/08|
|European Classification||C09D201/08, C09D5/18|
|19 May 1998||CC||Certificate of correction|
|17 Apr 2001||AS||Assignment|
Owner name: PMD HOLDINGS CORPORATION, A CORPORATION OF ILLINOI
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:B.F. GOODRICH COMPANY, THE, A CORPORATION OF NEW YORK;MITECH HOLDING CORPORATION, A CORPORATION OF DELAWARE;BFGOODRICH HILTON DAVIS, INC., A CORPORATION OF DELAWARE;AND OTHERS;REEL/FRAME:011485/0706
Effective date: 20010228
|31 Jul 2001||REMI||Maintenance fee reminder mailed|
|7 Jan 2002||LAPS||Lapse for failure to pay maintenance fees|
|12 Mar 2002||FP||Expired due to failure to pay maintenance fee|
Effective date: 20020106